Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G49/00—Compounds of iron
  • C01G49/0018—Mixed oxides or hydroxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G49/00—Compounds of iron
  • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G49/00—Compounds of iron
  • C01G49/02—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G51/00—Compounds of cobalt
  • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
  • C09C1/42—Clays
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/48—Conductive polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
  • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/20—Two-dimensional structures
  • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
  • Y10T428/24612—Composite web or sheet

Definitions

• the present invention relates to the use of an oxyhydroxysel related to the family of lamellar double hydroxides for the design and manufacture of an electrode for the storage of electrical energy.
• Ferric ferric oxyhydroxysels are intermediate compounds, related to the family of lamellar double hydroxides, which occur during the degradation of ferrous materials (steels) by ultimately turning into rust and are thus commonly known as green rust due to their color (Genin et al., Geoscience 2006).
• This product is therefore a natural product found particularly in flooded soils, the gleys, under the name of fougerite (mention Genin et al., Geochim, Cosmochim Acta 1998)
• the energy storage devices such as batteries, batteries or accumulators, harbor a chemical reaction between two substances, one of which can easily give up electrons (the reducer), and the other accept them (the oxidant). Such a reaction is called a reduction oxy.
• Each element of the oxidant / reducer pair constitutes an electrode.
• These electrodes when connected to an electrical consumption device, cause the flow of a current; the chemical reaction therefore produces a circulation of charges (electrons, ions).
• One of the objects of the invention is therefore to provide a material for the manufacture of an electrode for implementing energy storage devices such as batteries, batteries, accumulators or batteries. supercapacitors with energy performance far superior to the batteries, batteries, accumulators or supercapacities currently marketed, while having a production cost much lower than existing materials and can be eliminated without any adverse effect on the environment.
• Another aspect of the invention is to develop these active materials with the well-established composition by providing a manufacturing process either in the form of a film or a composite material mixed with carbon (graphite) thus making it possible to manufacture the storage devices 'energy.
• the present invention relates to the use of a material comprising at least one compound related to a ferric ferric double-layered hydroxyl (HDL), said compound comprising at least one divalent cation D ⁇ , and at least one trivalent cation T 111 , of formula following general
• a n ⁇ is an anion of charge n, n taking the values 1, 2 or 3, in particular 2, m is an integer ranging from 1 to 10, in particular from 1 to 4, advantageously 3, and x is comprised of 0 to 1, for the implementation of an electrode.
• At least one divalent cation D ⁇ means that the cation D ⁇ is used alone or in combination with another.
• the expression "at least one T 111 trivalent cation” means that the T 111 cation is used alone or in combination with another.
• the HDL-related compound requires the presence of a minimum proportion of Fe 11 of 1% to convert a Fe 11 ion into a Fe 111 ion. If the compound related to HDL does not contain Fe 11 , it is then non-functional.
• the invention more particularly relates to the use of a compound as defined above, in which the proportion of Fe 111 in the trivalent element is from 0% (m / m) to 100% (m / m). m) relative to the total amount of trivalent element.
• Fe 111 is not essential from the moment when Fe 11 capable of transforming into Fe 111 is present in the compound.
• the invention also relates to the use of a compound related to HDL as defined above, wherein D ⁇ is selected from Mg 11 , Ni 11 , Ca 11 , Mn 11 , Co 11 and Fe 11 and T 111 is selected from Al m , Co 111 , Cr 111 and Fe 111 .
• the present invention relates to the use of a material comprising at least one ferric ferric oxyhydroxy salt of the following general formula (II):
• a n " is an anion of charge n, n taking the values 1, 2 or 3, in particular 2, m is an integer varying from 1 to 10, in particular from 1 to 4, advantageously 3, and x is comprised of
• ferric ferric oxyhydroxysel can be partially modified by the partial or total substitution of at least one of its elements for the implementation of a non-polluting electrode.
• the ferric ferric hydroxyls belong to the family of lamellar double hydroxides which comprise cationic sheets comprising the Fe 11 and Fe 111 ions of structure
• Fe (OH) 2 so-called brucitic, and interlayers including anions and water molecules that counterbalance the excess positive charge due to Fe 111 ions.
• Ferric ferrous oxyhydroxysels have, for their part, a crystallographic structure substantially similar to that of the related hydroxy salts, but some of their ions OH "surrounding each cation Fe 111 are deprotonated by becoming O 2 ions" or, conversely, protonated in becoming water molecules. Fe 11 ions oxidize to Fe 111 to compensate for the charge and vice versa.
• ferric ferric oxyhydroxysels used in the context of the invention may be of natural origin or of synthesis, the latter hypothesis being favored.
• Fe 11 V Fe 11 + Fe 111
• Mössbauer spectrometry in the solid.
• FIGS. 2a1 show the evolution of Mössbauer spectra measured at 78 K of ferro ferric oxyhydroxycarbonate samples with different proportions of x which show the progressive disappearance of Fe 11 by transforming into Fe 111 .
• the ferrous doublets, D 1 and D 2 are transferred into the ferric doublet D 4 .
• Figures 2a, c, e, g, i represent the respective deconvolutions of the spectra of Figures 2b, d, f, h, j.
• a value of x greater than 0.66 it corresponds to a structure which would involve more energy to be achieved under natural conditions, while preferentially form magnetite, Fe3 ⁇ 4 7-Fe 2 Os, with a spinel structure.
• the crystallographic structure is metastable. This crystallographic structure is then obtained by voltammetric cycling.
• Voltammetric cycling is a method in which the voltage of the solid is varied with a potentiometer continuously cyclically.
• the term "metastable” refers to a system that corresponds to a local minimum of energy but where this minimum is not the lowest, leaving the latter the term of stable.
• anion refers to any negative charge ion.
• the anion has 1, 2 or 3 negative charges, and in particular 2 negative charges (for example carbonate).
• ferrous ferric simply becomes ferrous hydroxysel hydrated compound of the formula [Fe 3 ⁇ n ⁇ 6 H7N n] n + [A ⁇ n, m H 2 O] 11 ". It is then of a protonation during which OH " becomes H 2 O.
• the ferric ferric hydroxysel becomes the hydrated ferrous hydroxysel of formula [Fe 11 OO 1 2 Hi 4 ] 2+ A 2 -
• the ferrous hydroxysel ferric becomes simply the ferric oxyhydroxysel of formula [Fe 111 S n O 6n H 4n ] n + [A 1 " , m H 2 Of-.
• the ferric oxyhydroxysel becomes the ferric oxyhydroxysel of formula [Fe 111 OOi 2 H 8 ] 2+ A 2 " .
• each element of the oxidant / reducer pair is connected to an electrode.
• the ferric ferric oxyhydroxysel according to the invention has novel oxidation-reduction properties allowing the constitution of an electrode (anode or cathode).
• Electrodes for energy storage there are several technologies currently available to manufacture electrodes for energy storage, such as lead-acid battery, nickel-cadmium, nickel-metal hydride, nickel-zinc, lithium-ion ...
• non-polluting therefore refers to a material that does not have a priori compounds or contaminants that may have negative impacts on all or part of an ecosystem or the environment in general. Another advantage of the invention is therefore to require no removal of metal or treatment of the material before disposal, thus providing a non-polluting electrode.
• the invention relates to the use of the material defined above in which the theoretical specific electrical energy capacity of said electrode is greater than or equal to 160 Ah / kg, in particular 245 Ah / kg.
• One of the advantages of the material of the invention is to have a specific electrical energy capacity which is about 50% higher than the specific electrical energy capacities hitherto observed in the materials sold in particular Li-ion. and therefore has a potential power far superior to known electrode materials.
• the materials marketed to date only reach 160 Ah / kg, for example LiCoO 2 (The 14 th International Meeting on Lithium Batteries, June 22-28 th , 2008, Tianjin, China).
• the theoretical electrical energy capacity of the electrode defined above is from about 160 Ah / kg to about 300 Ah / kg, preferably from 160 Ah / kg to 250 Ah / kg, even more preferably from 200 Ah / kg to 250 Ah / kg, in particular 245 Ah / kg.
• the material used defined above can be implemented in energy storage devices such as batteries, batteries, accumulators or supercapacitors.
• energy storage device it is necessary to understand a device that can either only deliver the energy it contains to lead to a device that has no more energy and can not store it again. either to debit the energy it contains and then recharge energy to be able to charge it again.
• battery it is necessary to understand an energy storage device which modifies the chemical structure of its elements during operation but which can not return to their initial state. A battery thus has a limited duration of operation.
• battery it is necessary to understand an energy storage device that chemically modifies the surface of its elements which are immersed in an electrolyte, during operation, and which can then return to their initial state.
• accumulator is meant a device for storing electrical energy and which can restore it later.
• the material of the invention is capable of performing electric charges and discharges of varying duration depending on the substitutions made in the material and thus allowing its use either in batteries, batteries, accumulators or supercapacities.
• its essential advantage is to have a material having short charging and discharging times, of the order of a few minutes, thus making it possible to develop potential substitutes for supercapacitors, having a very large amount of electrical charge in particular. a minimum of time, essential characteristic especially for an electric car, compared to times of several days for lithium-ion batteries where it is necessary to be content with batteries of power.
• the invention relates to the use of a material defined above, in which A n ⁇ represents CO3 2 " leading to the following formula (III): [Fe ⁇ 6 (i- x ) Fe ⁇ i 6 X O 12 H 2 (7 _ 3x )] 2+ [CO 3 2 - , 3H 2 O] 2 - (III)
• x is from 0 to 1.
• the hydrated hydroxysal hydrate is the hydrated ferrous hydroxycarbonate of formula [Fe 11 OO 1 2 Hn] 2+ [CO 3 2 - , 3 H 2 O] 2 - .
• the ferric oxyhydroxysel is ferric oxyhydroxycarbonate of formula [Fe 111 OOi 2 H 8 ] 2+ [CO 3 2 " , 3 H 2 O] 2" .
• the material of the invention in which A n " represents CO 3 2" has a theoretical capacity of 245 Ah / kg, ie 800 Ah / L.
• Another advantage of the invention is therefore to provide a material having short charging and discharging times, of the order of a few minutes, thus making it possible to have supercapacitors, having a very large amount of electric charge in a minimum of time. , essential characteristic especially for an electric car, by comparison with times of several days for lithium-ion batteries where you have to settle for power batteries.
• the available protons H + OH " of the material defined above are partially or totally substituted by monovalent cations, in particular Li +, to give a structure of the following general formula (IV) in the case carbonate in which the protons are substituted with lithium:
• partially substituted is meant an exchange of a portion of the available protons by a monovalent cation, for example lithium.
• a monovalent cation for example lithium
• Another advantage of the substitution is to be able to use a lithium counter-electrode at -3 volts, as well as the corresponding electrolyte.
• the Fe 11 present in the material may be partially substituted by divalent cations, in particular Ni 2+ and / or Co 2+, to give a structure of the following general formula (V) in the case of carbonate in which the Fe 11 is substituted by Ni 2+ and the protons H are not substituted:
• partially substituted is meant an exchange of a portion of the Fe 11 atoms by a divalent cation such as nickel and / or cobalt from 1% to 50%, preferably from 1% to 40%, preferably from 1% to 30%, preferentially from 1% to 20%, preferably from 1% to 10%, preferably from 1% to 5%, especially 5%.
• the Fe 11 of the material of the invention may be substituted by a nickel atom, or a cobalt atom or both. It is understood that when the Fe 11 is substituted, the hydrogen atom of the groups
• OH " may also be substituted by a monovalent cation.
• the Fe 111 present in the material may be partially or totally substituted by trivalent cations, in particular Al + and / or Co +, to give a structure of the following general formula (VI) in the case of carbonate in which the Fe 111 is substituted by Al 3+ , and the Fe 11 and / or the H + protons are not substituted:
• the Fe 111 of the material of the invention may be substituted by an aluminum atom, or a cobalt atom or both.
• the advantage of the substitution here lies in changing the electrode potential and / or the stability of the material.
• the Fe 11 atom may also be substituted as indicated above as well as the proton of the OH " groups as indicated above or only the Fe 11 atom may be substituted as indicated above or else only the hydrogen atom of the OH " groups may be substituted as indicated above.
• the material defined above constitutes a cathode or anode depending on the choice of a counterelectrode present in said energy storage device.
• the operation of a battery, battery or supercapacity requires the presence of an anode and a cathode.
• the anode is the electrode where an electrochemical oxidation reaction leads to the production of electrons and constitutes the negative pole of the storage device.
• the cathode is the electrode where an electrochemical reduction reaction leads to the consumption of electrons and constitutes the positive pole.
• the counter-electrode is therefore the cathode and vice versa.
• the anode when the material of the invention is used as a cathode, the anode may then consist of a lithium or platinum electrode.
• the cathode is then made of other electrodes well known to those skilled in the art and usually used for other types of material constituting the active electrodes.
• Another advantage of the invention is therefore to be able to use the material either as cathode or as anode depending on the desired energy storage device by choosing the appropriate counter-electrode.
• said counter electrode used with the material of the invention has an active redox couple having a potential difference greater than 1 volt relative to the electrode containing said ferrous ferric oxyhydroxy salt.
• said material defined above is used in the form of a film deposited on a support, in particular a metal support such as steel, copper or an oxide such as tin oxide doped with indium (ITO) or a carbon support, in particular graphite, the thickness of the deposited film may vary between about 0.1 ⁇ m and 0.1 mm, preferably from about 10 ⁇ m thick to about 0.1 mm thick, in particular about 0.1 mm.
• the support may be metallic such as steel or copper or tin oxide or carbon such as graphite.
• the support is very important for the operation of the device storage since a film deposited on a gold or other support does not cause any signal in Môssbauer spectroscopy (FIG. 3).
• FIG. 4b shows the voltammetric curves obtained with a film of the invention containing 100 mg of material in the form of carbonate: Fe 111 OOi 2 HsCOs, that is to say (GR (COs 2 ' ) * or GR *) as defined above and deposited on a support.
• Another advantage of the invention is that it can easily constitute an electrode simply by depositing a film of the invention on a support.
• the thickness of the film defined above is 10 ⁇ m, preferably 20 ⁇ m, more preferably 30 ⁇ m, in particular 40 ⁇ m, in particular 50 ⁇ m, more preferably 60 ⁇ m, more preferably 70 ⁇ m. ⁇ m, more preferably 80 ⁇ m, in particular 90 ⁇ m, in particular 100 ⁇ m.
• said material defined above is used in the form of a composite and further comprises a binder such as oil or paraffin.
• composite is meant a mixture of carbon, especially graphite with the material of the invention.
• binder is meant a product that binds the graphite with the material of the invention to maintain the cohesion of the composite without obscuring a significant portion of the electrochemically active surface.
• binders can be used, in particular polymers containing groups giving rise to chemical or hydrogen bonds such as hydroxyl, carboxyl or amide groups.
• binders examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyacrylic acid, polyacrilamide, elastomers such as styrene / butadiene rubber. (SBR), acrylonitrile / butadiene (NBR).
• PTFE polytetrafluoroethylene
• PVDF polyvinylidene fluoride
• PAN polyacrylonitrile
• SBR styrene / butadiene rubber
• NBR acrylonitrile / butadiene
• the binders of the invention are chosen from oil or paraffin.
• FIG. 4a compares the voltammetric curves obtained with a composite of the invention based on carbon and containing 100 mg of material in the form of carbonate (GR *, ferric oxyhydroxycarbonate) as defined above, and with pure carbon .
• GR * ferric oxyhydroxycarbonate
• the binder used in the material defined above is paraffin and said composite material comprises a carbon matrix mixed with ferrous ferric oxyhydroxy salt, the ratio ferric ferric oxyhydroxysil / carbon (m / m) ranging from about 0.1 to about 100, preferably from about 0.1 to about 10, preferably from about 1 to about 10, and preferably from 8 to 10, and the ratio of ferrous ferric oxyhydroxy / ferric (par. m) being from about 1 to about 10, and preferably from about 8 to about 10.
• carbon matrix a source of powdered carbon which may be graphite but not limited to it.
• the proportion of the material of the invention with respect to the carbon is important for the proper functioning of the electrode.
• ferric ferric oxyhydroxy / carbon (m / m) a ratio ferric ferric oxyhydroxy / carbon (m / m) of about 0.1, the material will no longer be functional.
• ferric-ferric oxyhydroxysial ratio a ratio ferric ferric oxyhydroxy / carbon (m / m) of about 0.1
• (m / m) above defined may be from about more than 10 to about 100 and the material will have the same operating properties as when said above ratio is ⁇ 10 but will become more expensive to produce or even mechanically less resistant .
• the proportion of the material of the invention relative to the binder, in particular paraffin, is also important for the proper functioning of the electrode.
• the binder used in the material defined above is oil and said composite material comprises a carbon matrix mixed with ferrous ferric oxyhydroxy salt, the ferrous ferric oxyhydroxy / ferric oxime ratio (m / m). m) being from about 0.1 to about 100, preferably from about 0.1 to about 10, preferably from about 1 to about 10, and preferably from 8 to 10 and the ratio of ferrous ferric oxyhydroxysil to oil (m m) being from about 1 to about 10, and preferably from about 8 to about 10.
• the proportion of the material of the invention with respect to the carbon and with respect to the binder, in particular of the oil is important for the proper functioning of the electrode.
• the invention relates to the use of a material defined above, in which the cell of said storage device comprises an electrolyte, in particular an acid such as sulfuric acid or hydrochloric acid. in the case of carbonate or sulphate.
• electroactive material By “cell” it is necessary to understand all the different elements that constitute the energy storage device.
• electroactive material By “electrolyte” is meant any substance or compound which, in the liquid state or in solution, or in the form of gel allows the passage of electric current by displacement of ions and in particular protons.
• the invention relates to the use of a material as defined above in which the potential difference (ddp) of said cell of said storage device is from about IV to about 4V, preferably from about 3 V to about 4V, in particular 1.8V.
• the invention relates to a film deposited on a support, in particular a metal support such as steel, copper or an oxide such as indium-doped tin oxide (ITO) or a support carbon, in particular graphite and comprising at least one ferric ferric oxyhydroxysel of general formula (I), (II), (III), (IV), (V) or (VI) defined above and, wherein A n ⁇ is an anion of charge n, n taking the values 1, 2 or 3, in particular 2, m is an integer ranging from 1 to 10, in particular from 1 to 4, advantageously 3, and x is from 0 to 1; , the thickness of the deposited film may vary between about 0.1 microns and 0.1 mm.
• a metal support such as steel, copper or an oxide such as indium-doped tin oxide (ITO) or a support carbon, in particular graphite and comprising at least one ferric ferric oxyhydroxysel of general formula (I), (II), (III), (IV),
• the invention relates to a composite comprising at least one ferric ferric oxyhydroxysel of general formula (I), (II), (III), (IV), (V) or (VI) defined above and in which A n ⁇ is an anion of charge n, n taking the values 1, 2 or 3, in particular 2, m is an integer ranging from 1 to 10, in particular from 1 to 4, advantageously 3, and x is included from O to l.
• the composite defined above further comprises a binder, especially oil or paraffin.
• the invention relates to a composite defined above, wherein said binder is paraffin and said composite material comprises a carbon matrix mixed with ferrous ferric oxyhydroxy salt, the ferrous ferric oxyhydroxysial ratio / carbon (m / m) being from about 0.1 to about 100, preferably from about 0.1 to about 10, preferably from about 1 to about 10, and preferably from 8 to 10, and the ratio of ferrous oxyhydroxys ferric / paraffin (m / m) being from about 1 to about 10, and preferably from about 8 to about 10.
• the invention relates to a composite defined above wherein said binder is oil and said composite material comprises a carbon matrix mixed with ferrous ferric oxyhydroxy salt, the ferrous ferric oxyhydroxysil ratio the carbon (m / m) being from about 0.1 to about 100, preferably from about 0.1 to about 10, preferably from about 1 to about 10, and preferably from 8 to 10, and the ferrous oxyhydroxys ferric / oil (m / m) being from about 1 to about 10, and preferably from about 8 to about 10.
• the invention relates to a film or composite defined above, in which A n ⁇ represents CO3 2 " .
• FIGS. 5, 6a and 6b compare the Môssbauer spectra obtained with a GR * (1) reference (obtained by violent oxidation of a ferrous ferric hydroxycarbonate according to Example 2) and a material of the invention in the form of a composite with 50 mg of GR * (1) ( Figure 6a) and 100 mg of GR * (1) ( Figure 6b) respectively.
• the spectra obtained are similar whether reference or composites and whatever the amount of material used. In addition, this indicates that even after redox cycles, the materials of the invention have properties similar to those they originally had.
• Table I shows the hyperfine parameters measured at room temperature for the two composites and the GR * (1) reference.
• the film or the composite defined above is used as cathode or anode of an energy storage device according to the choice of the counter-electrode.
• the invention relates to an energy storage device such as battery, battery, accumulator or supercapacitor comprising a cathode or anode consisting of a film or a composite defined above.
• the energy storage device such as battery, battery, accumulator or supercapacity defined above, furthermore comprises an electrolyte, in particular an acid such as sulfuric acid or hydrochloric acid in the case of carbonate or sulphate.
• the present invention relates to an energy storage device such as a battery, battery, accumulator or overcapacity defined above, comprising: at. an anode consisting of ferric ferric oxyhydroxysel in which the anion is divalent, and in particular is sulphate (SO 4 2 " ) or carbonate (CO 3 2 ), b) a metal iron cathode, ie an electrolyte, especially under form of gel or solution, at pH below 5, in particular at a pH of 2 or 3.
• an anode consisting of ferric ferric oxyhydroxysel in which the anion is divalent, and in particular is sulphate (SO 4 2 " ) or carbonate (CO 3 2
• a metal iron cathode ie an electrolyte, especially under form of gel or solution, at pH below 5, in particular at a pH of 2 or 3.
• the electrodes correspond to the Fe (O) / Fe (II) pair with respect to the Fe (II) / RV * Fe (III) pair in an acidic electrolyte around pH 2 (see FIGS. 7A and 7B).
• the present invention relates to a method for implementing an energy storage device such as a battery, battery, accumulator or supercapacity comprising a protonation or deprotonation step of the material defined above.
• the material of the invention then constitutes a cathode.
• accumulators or supercapacitors these two functions alternate, depending on whether the device is charging current or charging.
• the invention relates to a method for manufacturing a composite defined above, comprising the following steps: a. Mixing in a ferrous ferric oxyhydroxysel carbon matrix of general formula (I), (II), (III), (IV), (V) or (VI) defined above, to obtain a ferrous matrix-oxyhydroxysel mixture ferric, b. Heating at a temperature of from about 30 ° C. to 90 ° C., preferentially from about 45 ° C. to 80 ° C., preferably from about 60 ° C. to 70 ° C., in particular 60 ° C. of said mixture with oil or paraffin to obtain a composite.
• the invention relates to a process for manufacturing a film defined above, comprising a step of depositing the material, either chemical or electrochemical in the aqueous or dry phase, or by "spindropping",
• the chemical or electrochemical deposition process provides a more stable film when immersed in an electrolyte solution (0.04M NaHCOs).
• the method of manufacturing a film comprises the following steps: a. depositing a thin layer of about 0.1 ⁇ m thick to about 0.1 mm thick, preferably about 10 ⁇ m thick to about 0.1 mm thick, in particular about 0, 1 mm ferric ferric oxyhydroxysel of general formula (I), (II), (III), (IV), (V) or (VI) defined above, on a support as defined above, to obtain a ferrous ferric oxyhydroxysel supported, b. drying at a temperature of from about 15 ° C to 40 ° C, preferably from about 20 ° C to 30 ° C, in particular from about 20 ° C to about 25 ° C of the product obtained in the previous step for get a movie.
• FIGS. 1 a a show the Mössbauer spectra obtained respectively at a temperature of 16, 50, 60 and 78 K with the material (GR *), ferric oxyhydroxycarbonate of formula [Fe 111 OOi 2 Hs] 2+ COs 2 " and prepared by violent oxidation with H 2 O 2 ferric ferric hydroxycarbonate [Fe ⁇ 4Fe i ⁇ 2 (OH) i 2 ] 2+ C ⁇ 3 2 ⁇ of Example 2.
• the ordinate axis corresponds to the transmittance in% and the abscissa axis corresponds to the speed in mm / s.
• the ordinate axis corresponds to the transmittance in% and the abscissa axis corresponds to the speed in mm / s.
• Figures 2a, c, e, g, i represent the deconvolutions of the afferent spectra, b, d, f, h, j: the relative abundances of components are indicated.
• FIG. 3 represents the Môssbauer spectrum obtained at room temperature with the material of the invention (GR *) in the form of a film deposited on a gold substrate.
• the ordinate axis corresponds to the intensity in arbitrary units and the abscissa axis corresponds to the speed in mm / s.
• 4a-b represent the voltammetric curves obtained from the GR * material, the ferric oxyhydroxycarbonate, [Fe ⁇ i 6 ⁇ i 2 H 8] 2 + [CO 3 2 ", 3 H 2 O] 2" in different forms 100 mg of GR *.
• FIG. 4a represents the curve obtained with a composite of GR * with carbon (solid line) of Example 3 or a reference of carbon alone (dashed lines).
• the ordinate axis corresponds to the current obtained in ⁇ A and the abscissa axis corresponds to the potential in volts.
• Figure 4b shows the curve obtained with a GR * film of Example 4 (the solid lines and dashed lines corresponding to two cycles).
• the ordinate axis corresponds to the current obtained in ⁇ A and the abscissa axis corresponds to the potential in volts.
• FIG. 5 represents the Môssbauer spectrum obtained with the reference material of the invention (GR *).
• the ordinate axis corresponds to the intensity in arbitrary units and the abscissa axis corresponds to the speed in mm / s.
• Figures 6a-b show the Môssbauer spectrum obtained with the material of the invention (GR *) in the form of a composite.
• Figure 6a corresponds to the carbon composite with 50 mg of GR *.
• the ordinate axis corresponds to the intensity in arbitrary units and the abscissa axis corresponds to the speed in mm / s.
• Figure 6b corresponds to the carbon composite with 100 mg GR *.
• the ordinate axis corresponds to the intensity in arbitrary units and the abscissa axis corresponds to the speed in mm / s.
• FIGS. 7A and 7B are the so-called Eh-pH diagram of Pourbaix of all the compositions of ferric ferric oxyhydroxycarbonate RV * (x) (or GR * (x)) of general formula Fe 11 O (I- * ) Fe 111 O * O 12 H 2 (7-3 * ) CO 3 .
• the Pourbaix diagram consists of a set of parallel straight lines of slope -0.0591 (Nernst's law). It can be compared to that of stoichiometric green RV (or GR) rust, which is useful in the corrosion of ferrous materials.
• FIG. 7A shows the Pourbaix diagram of the hydroxy carbonate Fe 11 "111 , [Fe H 4 Fe i ⁇ 2 (OH) i 2 ] 2+ [CO 3 2" , 3H 2 O] 2 " in dissolution mode -precipitation.
• the green rust layer RV dissolves at the end of the aqueous oxidation to precipitate again in the form of ferric oxyhydroxide, FeOOH, which depending on the medium may be the goethite ⁇ -FeOOH, the lepidocrocite ⁇ -FeOOH, ⁇ '-FeOOH ferrihydrite or even ⁇ -FeOOH akaganite.
• FeOOH ferric oxyhydroxide
• Mossbauer reflection spectroscopy using the MIMOS apparatus was used to determine the oxidation state of iron in composites and films.
• the MIMOS device operates by backscattering geometry to detect re-radiated radiation (14.4 keV for gamma-rays and 6.4 keV for X-rays).
• MIMOS is also used to study the iron compounds present on the soil of the planet Mars. (NASA and European Space Agency) Môssbaurer spectra were calibrated using an iron sheet at room temperature and were fitted with Lorentzian-shaped lines and a single ferric quadrupole doublet.
• Ferric ferric hydroxycarbonate stoichiometric [Fe ⁇ 4Fe ⁇ i 2 (OH) i 2 ] 2+ C ⁇ 3 2 ⁇
• GR (CO3 2 " ) is prepared by chemical synthesis, either by oxidation of a precipitate of Fe (OH) 2 in the presence of carbonate ions as described by Genin et al (2006, Geoscience), or by co-precipitation of Fe 11 and Fe 111 ions in the presence of anions as described by Ruby et al (2006, Geoscience).
• ferric ferric hydroxycarbonate is then deprotonated completely with a violent oxidant such as H 2 O 2 in excess (GR * (I)) or air after drying (GR * (2)), as described in Genin et al. (2006, Geoscience) to form ferric oxyhydroxycarbonate of formula [Fe ⁇ i 6 0i 2 H 8 ] 2+ CO 3 2 - (GR * (1) or (2)).
• a violent oxidant such as H 2 O 2 in excess (GR * (I)
• GR * (2) air after drying
• Môssbauer vibration spectrometry (Raman or infra red) and transmission electron microscopy.
• a and ⁇ A quadrupole difference and standard deviation ⁇ : displacement of the quadrupole
• Table II shows that GR (CO 3 2 " ) is paramagnetic below 12 K. Its Mossbauer spectrum has three doublets at 12 K (Z) 1 , D 2 and D 3 ) D 1 and D 2 correspond to Fe ions 11 and D 3 correspond to Fe 111 ions.
• GR * (1) obtained by violent oxidation shows no trace of Fe 11 ions confirming the total oxidation of GR (CO 3 2 " ).
• GR * (2) obtained by oxidation in the air does not show any traces of Fe 11 ions either.
• the Mössbauer spectra of (GR * (1) obtained at 16 K, 50 K, 60 K and 78 K are represented in FIGS. 1a, 1b, 1c and 1d.
• the oxyhydroxy carbonate (GR * (I)) and the powdered carbon are mixed with paraffin or oil as a binder.
• paraffin the composites are manufactured by mixing 250 mg of carbon and 50 or 100 mg of GR * (1), then the mixture is heated in the presence of 100 mg of paraffin to bind the whole.
• Thin films of GR * (1) were prepared on carbon supports or metal supports or oxide supports such as indium-doped tin oxide (ITO) by chemical or electrochemical deposition. a fine sediment then drying at 60 0 C or "spindropping" of a fine sediment then drying at room temperature.
• ITO indium-doped tin oxide
• the voltammetric curves of the composites and films were obtained using these materials as the working electrode.
• An Ag / AgCl electrode was used as the reference electrode for composites characterization and a pseudoreference was used for the films. These electrodes were kept in contact with 0.04M NaHCCh solution. The pH of the solution was buffered to 8-9 with carbonate. Electrochemical studies were performed on an Autolab PGSTAT 12 potentiostat controlled with PGES software for voltage scanning.
• the electrolyte is an acid solution with a pH of less than 5, preferably 2 (for example sulfuric acid or hydrochloric acid).
• Another advantage of the material of the invention is that it allows the manufacture of batteries whose weight is five times lighter than that of lead batteries.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Power Engineering (AREA)
• Inorganic Chemistry (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Dispersion Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Electric Double-Layer Capacitors Or The Like (AREA)
• Compounds Of Iron (AREA)
• Secondary Cells (AREA)
• Primary Cells (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (2)

Family

ID=40433767

Family Applications (1)

Country Status (7)

Cited By (2)

Families Citing this family (9)

Citations (3)

Family Cites Families (1)

• 2008
  • 2008-07-29 FR FR0804325A patent/FR2934718B1/fr active Active
• 2009
  • 2009-07-28 JP JP2011520568A patent/JP2011529618A/ja active Pending
  • 2009-07-28 US US13/056,769 patent/US9051190B2/en active Active
  • 2009-07-28 CN CN200980134082.6A patent/CN102143917B/zh active Active
  • 2009-07-28 EP EP09740398.4A patent/EP2315722B1/fr active Active
  • 2009-07-28 BR BRPI0916586A patent/BRPI0916586A2/pt not_active IP Right Cessation
  • 2009-07-28 WO PCT/FR2009/051514 patent/WO2010012951A2/fr active Application Filing
• 2014
  • 2014-09-01 JP JP2014177189A patent/JP6149014B2/ja active Active
• 2016
  • 2016-12-27 JP JP2016253738A patent/JP2017126561A/ja active Pending

Patent Citations (3)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events